Treatment of cellulosic fiber containing fabrics to improve the physical characteristics

ABSTRACT

A TREATMENT OF CELLULOSIC FABRICS AND FABRICS CONSTRUCTED OF BLENDS OF CELLULOSIC AND NON-CELLULOSIC SYNTHETIC FIBERS, WHEREBY THE DURABILITY OF THE FABRICS IS RETAINED EVEN AFTER REPEATED LAUNDERINGS WHILE THE &#34;HAND&#34; OF THE FABRICS IS MUCH IMPROVED OVER THAT OBTAINED BY PRIOR TREATMENTS. THIS TREATMENT CONSISTS OF THE APPLICATION TO THE FABRICS OF A COMPOSITION CONTAINING, AS THE ACTIVE INGREDIENT, A MIXTURE OF METHYLOLATED METHYL CARBAMATE WITH EITHER (A) METHYLOLATED METHOXYETHYL CARBAMATE, OR (B) METHYLOLATED HYDROXYETHYL CARBAMATE, OR (C) METHYLOLATED N-PROPYL CARBAMATE WHEREIN THE PERCENTAGE OF THE METHYLOLATED METHYL CARBAMATE IS ABOUT FROM 10 TO 70 MOL PERCENT AND OF THE OTHER COMPONENT IS BETWEEN ABOUT 90 TO 30 MOL PERCENT.

TREATMENT OF CELLULOSIC FIBER CONTAIN- ING FABRICS TO IMPROVE THE PHYSICAL CHARACTERISTICS Angelo J. Ramunda, deceased, late of Fairlawn, N..I., by Phyllis G. Ramunda, executrix, Fairlawn, N.J., Phillip Adams, Murray Hill, Sidney Beinfest, Berkeley Heights,

and Thaddeus A. Gnlakowski, Ridgefield, N.J., assignors to Millmaster Onyx Corporation, New York, N.Y. No Drawing. Continuation-in-part of abandoned application Ser. No. 789,916, Jan. 8, 1969. This application a May 19, 1971, Ser. No. 145,042 a l Int. Cl. D06m 13/12 ABSTRACT OF THE DISCLOSURE A treatment for cellulosic fabrics and fabrics con structed of blends of cellulosic and non-cellulosic synthetic fibers, whereby the durability of the fabrics is retained even after repeated launderings while the hand" of the fabrics is much improved over that obtained by prior treatments. This treatment consists of the application to the fabrics of a composition containing, as the active ingredient, a mixture of methylolated methyl carbamate with either (a) methylolated methoxyethyl carbamate, or (b) methylolated hydroxyethyl carbamate, or methylolated n-propyl carbamate wherein the percentage of the methylolated methyl carbamate is about from to 70 mol percent and of the other component is between about 90 to 30 mol percent.

This is a continuationin-part of copending application Ser. No. 789,916, filed Jan. 8, 1969, now abandoned. This invention relates to a method and composition for treating textiles, and it particularly relates to the treatment of fabrics made from cellulosic fibers or blends of cellulosic and non-cellulosic synthetic fibers for the purpose of providing satisfactory durability (ability to withstand abrasion, stretch, strain, etc.) as well as providing a very good hand, after repeated launderings.

It has heretofore been proposed to utilize a mixture of methylolated n-propyl and isopropyl carbamate resins for the present purpose. However, although the wash-wear and durability properties of such compositions were, in general, highly satisfactory, it was found that the hand of the treated fabrics was somewhat papery was unpleasant to the touch. This hand was greatly improved by the compositions of the present invention. Furthermore, the isopropyl carbamate component is quite costly.

It is known that methylolated methyl carbamate will generally provide satisfactory results in the treatment of textile fabrics. However, it has been found that the use of such methylolated methyl carbamates, by themselves, is objectionable because it results in a fishy odor or in other odors such as that of formaldehyde. This odor can only be eliminated by after-washing the cured fabric. Furthermore, methylolated methyl carbamates, by themselves, cause the development of discoloration when subjected to the customary high temperatures used in short-time curing operations. a t

In accordance with the present invention, it has now surprisingly been discovered that mixtures of methylolated methyl carbamate with either methylolated methoxyethyl carbamate, methylolated hydroxyethyl carbamate, or methylolated propyl carbamate, and preferably the latter, wherein the percentage of the methylolated methyl carbamate is in the range of about 10-70%, preferably 40- 60% of the mixture, and the percentage of the other component is in the range of about 30 to 90 mol percent, results in a composition which may be applied to fabrics and cured at either the normal high temperatures or at 3,752,697 Patented Aug. 14, 1973 bamates separately, and combine them in the required proportions; or the methyl carbamate may be mixed with either n-propyl carbamate, hydroxyethyl carbamate, or methoxyethyl carbamate, and the mixture then methylolated together, as described in the following examples. There are advantages, for example, in employing certain mixed carbamates which are liquid, although their components are solid, as disclosed in US. Pat. No. 3,014,807. These mixtures may be used as such, or they may be used along with a sufiicient quantity of ether component to arrive at the desired mol ratio.

The following examples are illustrative of the invention, with no intent, however, to limit the invention except as claimed EXAMPLE 1 An agitated three-necked flask, fitted with a thermometer and a reflux condenser, was charged with grams (one mol) of methyl carbamate, 103 grams (one mol) of n-propyl carbamate, 324 grams (four mols) of 37% aqueous formaldehyde, 243 grams of Water, and a requisite amount of 25% aqueous NaOH to bring the pH to 10.0:L-.05. The mixture was maintained at 50-53 C., under agitation, at atmospheric pressure, for four hours, or until the reaction was complete. The product consisted largely of the dimethylol derivatives of the alkyl carbamate mixture. The pH was then reduced to 6.065 by the careful and gradual addition of concentrated hydrochloric acid.

The mol ratio of dimethylolmethyl carbamate to dimethylol-n-propyl carbamate was therefore 1:1, and the active content was 40% by weight as dimethylol alkyl carbamates.

EXAMPLE 2 In the same manner as in Example 1, grams (1.2 mols) of methyl carbamate, 82.4- grams (0.8 mol) of n-propyl carbamate, 324 grams (four mols) of 37% aqueous formaldehyde and 235 grams of water were reacted. The mol ratio of methylolated methyl to n-propyl carbamates was therefore, 1.5 :1, and the active content was 40% by weight.

EXAMPLE 3 Similarly to Example 1, 60 grams (0.8 mol) of methyl carbamate and 123.6 grams 1.2 mols) of n-propyl carbamate were reacted with four mols of aqueous formaldehyde in 251 grams of water. The ratio of methylolated methyl carbamate to n-propyl carbamate was therefore 1:15. The active content of dimethylolated carbamates was 40% by weight.

EXAMPLE 4 In the manner of Example 1, a 40% active solution of a dimethylolated 50:50 mixture of methyl carbamate and methoxyethyl carbamate was prepared. Instead of an equimolar mixture, any desirable proportion may be dimethylolated in the same way. The same solution may be prepared using hydroxyethyl carbamate instead of the methoxyethyl carbamate.

The products of Examples 1, 2, 3 and 4 and also, as controls, 40% aqueous solutions of the corresponding dimethylol derivatives of n-propyl carbamate and of methoxyethyl carbamate (about 52:48) were applied to fabrics of cotton broadcloth, cotton twill and 65/35 Dacron polyester/cotton broadcloth by padding them in a bath containing 22.5 parts by weight of the respective methylolated carbamate (hereinafter referred to as reactant) and a mixed zinc-magnesium salt catalyst, in the parts by weight indicated in each case in the following tables, the balance being water.

Although the mixed zinc-magnesium salt catalyst used [Fabric: 100% cotton broadcloth. Catalyst: 4%. Wet

TABLEI V piekiipf 55-65%. Cure: 14"- F., two minutes. B-340 F., two'rninutesl WJW. Cl. ret. T Flex 1 percent Reactant Cure. Tensile Tear abrasion CARP wash washes loss 33 512 223 229 I 3. 3 3. 2 27 320 136' 2571 .-3.9 3.7 33 498 231 227 3.3 3. B 27 336 138 262 4. 2 4. A. 34 464 242 239 3.5 3. B 28 320 130 260 3.9 3. A 31 480 225 235 3.4 3. y B 26 288 143 s I 4.0 4.

A. 32 480 237 235 3.5 3. 1:1.5 B 26 320 127 261 4.0 3. Me/MEC. A 33 490 221 249 3.5 3. Mc/MEC.... B 27 3l0 139 261 3.2;. 3.1 1.5

Nora-Shrinkages were acceptable for all samples. Chlorine damage was evaluated after five commercial launderings with acid sour, using zinc silicofluoride. N o discoloration was noted on any sample after chlorination and subsequent scorching. v

in this example is preferred, other catalysts may be substituted. As, for example, the chloride, nitrate, sulfates and fiuoborate salts of Group II elements, such as magnesium and zinc.

EXAMPLE 5 In the manner of Example 1, dimethylolated methyl-, n-propyland -methoxyethyl carbamates were prepared singly and separately, and finished at 40% activity by weight. Mixtures of the methylolated methyl carbamate were then prepared with each of the above homologs in the desired mol ratios.

It is to be understood that 40% activity by weight is merely a matter of convenience, and other concentrations may be prepared within reasonable limits in order to facilitate the preparation of textile treating baths, with or without the addition of auxiliaries.

In the following tables, the n-propyl carbamate reactant is abbreviated to Pr; the methoxyethyl carbamate reactant is abbreviated to MEC; the products of Examples 1, 2 and 3 are designated by their respective ratios of methyl to propyl components,'i.e., 1:1, 1.5:1 and 111.5; the mixture of methyl and methoxyethyl is indicated as Me/MEG. For the purpose of comparing these reactants, other auxiliaries frequently used, such as lubricants, softeners, wetting agents and resinous materials which contribute to such desirable qualities as hand, durability and the like, have been omitted. The properties listed in the following tables are therefore dependent only on the basic components of this invention and not on the, inclusion of'any additives. It will, therefore, be appreciated that these listed properties may be, in some cases at least, significantly enhanced by the inclusion of such auxiliaries. In each case, the fabric was padded in the bath to the indicated wet pickup, dried for a period of between about two and four minutes at a temperature of betweenabout 250 F. and 350 F., and cured for a period of between one-half minute and two minutes at a temperature of between about 300 F. and 400 F.

The following testing methods were used in the examples given hereinafter:

From the Federal Specification, Textile Test Methods:

(1) Tensile strength (pounds, fill)--Method CCC- (2) Tearing strength (grams, fill)Method CCC- (3) Flexing abrasion resistance /t" x 2", fill)- Method CCC-T191B-5300 From the 1964 Technical Manual of the American Association of Textile Chemists and Colorists:

(1) Crease-angle retention rating (warp+fill) AATCC Method No. 88-C1964T The range of 40%-60%"for' Me/Pr in the above table, the preferred range, shows nosignificant variation-The same is true for Me/MEC, which is reported above for /50 composition only. 1

TABLE 11 [Fabric: 100% cotton twill. Catalyst: 5.5%. Wet pickup: -70%. Cure A"270300 F., two minutes. B340 F.', two minutes] Flex 1 1 5 Reactant Cure Tensile Tear abrasion CA R wash washes B A 51 832 274 248 4. 3 3. 9 B 43 704 253 261 3. 9 3. 9 A 53 960 281 260 4. 3 3. 2 B 43 960 247 262 4. 3 4. 9 A 51 960 298 242 4. 2 3. 1 B 38 928 259 '254 4. 2 4. 9 A 48 896 265 259 4. 2 3. 2 B 46' 768 233 265 4. 0 4. A 54 832 293 246 4. 0 4. Q

B 43 896 277 267 4. 0 4. A 49 940 296 252 4. 2 4. O Me/ME C- B 43 925 250 250 4. 1 4. 0

N oTn.-Shrinkage in every case was less than 1%. The range of 40%- for Me/Pr in the above table, the preferred range, shows no signifi- 4 cant variation. The same is true for Me/MEC, which is reported above for 50/50 composition only.

TABLE III [Fabric: /35 Dacron/cotton broadcloth. Catalyst: 7%. Wet pickup: 55- 60%. Cure: A.340 F., three minutes. B-400 F., thirty seconds] Shrinkage, warp-fill 1 5 Reactant Cure 1 wash 5 washes CAR" wash washes 0. 5-0 0.5-0 283 4. 1 4. l 1. 0-0 1. 0-0 293 4. 3 4. 2 1. 0-0 1. 0-O 282 4. 3 4. 0 0. 5-0 1. 0-0 291 4. 4 4. 2 0. 5-0 1.0-0 281 4. 2 4. 2 0.5-0 0.5() 291 4.4 4.3 1. 0-0 1. 0-0 280 4. 2 4. 2 0. 5-0 0.5-0 294 4. 4 4. 3 0.5-0.5 0.5-0. 5 280 4. 1 4. 0 1. 00 1. 0-0. 5 294 4. 4 4. 3 60 0. 5-0 .0. 5-0 280 4. 2 4. 0 Me/MEC--. B 1. 0-0 0.5-0 287 4. 3 4. 2

65 The above examples and data tables include mixtures of methyl and methoxyethyl. Comparable results are also obtained when substituting hydroxyethyl for the rhethoxyethyl component.

Although the invention is described above with the utilization of methylolated methyl carbamate as one of the essential components, this bein the preferred form of the invention, it is also possible, although least preferable at this time, to substitute methylolated hydroxyloweralkyl carbamates for the methylolated methyl carbmate; as for example, methylolated hydroxyethyl, methylolated hydroxy-n-propyl, methylolated hydroxyisopropyl or methylolated hydroxy-butyl carbamate. In such case, of course, the methylolated hydroxyethyl carbamate cannot be used as the second component when it is used as the first component.

The invention claimed is:

1. A method of treating fabric which comprises applying to the fabric an aqueous composition consisting essentially of methylolated methyl carbamate in admixture with either (a) methylolated hydroxyethyl carbamate, b) methylolated methoxyethyl carbamate, or (c) methylolated n-propyl carbamate, wherein the percentage of the methylolated methyl carbamate is between about 10 to 70 mol percent and the percentage of the other component is between about 90 to 30 mol percent, drying the treated fabric, and then curing the dried fabric.

2. The method of claim 1 wherein the percentage of the methylolated methyl carbamate is between about 40 to 60 mol percent.

3. The method of claim 1 wherein the drying is effected at a temperature of about 250 F. to 350 F., and the curing is effected at a temperature of about 300 F. to 400 F.

4. The method of claim 1 wherein the aqueous composition also includes an elfective amount of a catalyst.

5. A fabric of cellulosic fibers or blends of cellulosic and non-cellulosic synthetic fibers, wherein the fabric is treated by the method of claim 1.

References Cited UNITED STATES PATENTS 3,420,696 1/1969 Cotton et al 117-139.4 X 3,416,880 12/1968 Kullman et al. 8-116.3 3,219,632 11/1965 Frick et al. 8-116.3 X 3,014,807 12/1961 Beinfest et al. 106-162 3,565,680 2/1971 Ramnnda et al. 117-1394 X 3,454,423 7/1969 Cohen et a1 117-1395 3,402,989 9/1968 Canter et al. 8-116.3 3,622,261 11/1971 Cotton et al. 8-116.3 X 3,144,299 8/1964 Frick et al 8-116.3 3,424,724 1/ 1969 Nordstrom 117-161 X 3,497,471 2/1970 Cohen et al. 1 17-1394 X 20 WILLIAM D. MARTIN, Primary Examiner H. I. GWINNELL, Assistant Examiner U.S. Cl. X.R.

1-17-139.4, 139.5 A, 143 A, 16 'LN; 260-29.4 R 

